This proposal describes several novel synthetic approaches to functional and structural analogs of the naturally occurring mitomycins. The synthetic routes proposed employ new synthetic designs in which well-known photochemical and thermal reactions are used to construct the basic pyrroloindoloquinone backbone, present in the mitomycins, from readily preparable starting materials. The analogs to be synthesized will contain functional groups that serve to mimic those in the natural materials presumed to be responsible for their drug activities. The mitomycins, especially mitomycin C, are known to possess potent anti-tumor activities, but unfortunately high toxicities. Thus, the aim of our synthetic program is to develop efficient routes for preparation of analogs with potentially higher activity to toxicity ratios. The synthetic designs chosen for investigation and, thus, guiding the course of the proposed research are outlined as follows: 1. Photochemical di-pi-methane rearrangement of N-vinyl-2-pyridones followed by thermal rearrangement of the intermediate aza tricyclic dienones to the pyrrolizidine ring systems present in the mitomycins. 2. Reaction of azabicyclo (3.1.0) alkanes and their substituted derivatives with beta-chloroenones through an additional ring expansion sequence to again produce substituted pyrrolizidines. 3. Electrocyclization of 1,2-dihydroazocinylanions, prepared by reaction of substituted acetylenes with N-blocked 1,2-dihydropyridines followed by anionic deblocking, to substituted pyrrolizidines. 4. Structural and functional elaboration of the compounds produced in order to prepare mitomycin analogs.